Preparation of improved motor fuel



Feb. 17, 1953 D. E. BURNEY ETAL ,62

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. Motor? Patented Feb. 17, 1953 PREPARATION OF IMPROVED MOTOR FUELDonald E. Burney, Griffith, and Bernard H. Shoemaker, Hammond, Ind.,assignors to Standard Oil Company, Chicago, 111., a corporation ofIndiana Application November 29, 1947, Serial No; 788,845

Our invention relates to the preparation of superior motor fuels fromolefin copolymers.

More particularly, it relates to a method for reacting secondaryolefin-tertiary olefin copolymers with carbon monoxide and hydrogen andobtaining thereby a sensitive motor fuel of high performance number.

The determination and specification of gasoline quality is a problemthat has occupied the attention of automotive engineers for many Atpresent, one particular phase of gasoline quality is expressed in termsof octane numbers, or preferably in terms of perform- On octane numberis an antiknock rating of a gasoline in terms of the percentage ofisooctane (2,2,4-trimethylpentane) in a binary mixture of isooctane andn-heptane which exhibits knocking at the same compression ratio as thegasoline under specified test conditions. A performance number, on theother hand, is the knock-limited power output obtainable from a givengasoline under the test conditions, expressed in terms of percentage ofthe power obtainable with pure isooctane under the same test conditions.(See Brooks, Development of Reference Fuel Scales for Knock Rating,

S. A. E. Journal, 54, 394-403, August 1946.) Performance numbers are asuperior index of gasoline quality, since unlike octane numbers, they donot suffer a discontinuity at the 100 level. They may be determined by avariety of test methods, of which the two most commonly used are theASTM-CFR Motor method and the CFR Research method, commonly designatedASTM and CFR Research, respectively. These two methods do not ordinarilygive the same performance numbers for a given gasoline; in fact, thedifference between the two ratings for a given gasoline is a furthermeasure of its quality, called the sensitivity of the gasoline,

which is defined as the CFR Research rating minus the ASTM Motor rating.In general, it has been found that of two gasolines having the same ASTMMotor rating, the one having the higher sensitivity will give the betterroad performance. Sensitive fuels are particularly well adapted to usein aircraft engines, especially fighter planes, where their superiorresponse to large power demands is a distinct advantage.

Our invention makes use of the so-called x0 reaction wherein an olefinis converted first into an aldehyde by reaction with carbon monoxide andhydrogen at elevated temperature and pressure in the presence of an ironor cobalt catalyst, v:

9 Claims. (Cl. 260604) CHO and the aldehyde is subsequently hydrogenatedby conventional methods to the corresponding alcohol,

H HO H HzOH Our invention" is based on'the discovery that carbonmonoxide and hydrogen react only partially under 0x0 process conditionswith the gasoline-boiling-range olefinic products resulting from thecopolymerization of secondary olefins with tertiary olefins, leavingunaffected an olefin fraction which, on being hydrogenated, is convertedinto a saturated hydrocarbon mixture of high performance number and highsensitivity.

One object of our invention is to provide a convenient means forsegregating olefin copolymers into useful fractions. Another object ofour invention is to separate a sensitive motor 'fuel of high performancenumber from secondary olefin-tertiary olefin copolymers. Other objectsof our invention, and its advantages over the prior art, will beapparent from the following description and examples.

Numerous methods have been devised for the polymerization andcopolymerization of olefins to produce higher-boiling materials usefulprimarily as ingredients of high quality gasolines. Various chargingstocks hav been utilized, comprising a mixture of the normally gaseousolefins and inert materials, such as paraffin hydrocarbons. In general,the processes employ acidic catalysts, such as sulfuric acid, phosphoricacidjor hydrogen fluoride; potentially acidic catalysts such as copperpyrophosphate or boron fluoride; or solid catalysts such assilica-alumina or acidtreated bentonite. Hot sulfuric acid (MO-194 F.),for example, absorbs isobutylene and nbutylene from mixtures ofisobutylene, n-butylenes, and inert materials, and produces a primarilydimeric product containing substantially all of the isomerictrimethylpentenes and dimethylhexenes.

In an especially successful and convenient polymerization process,secondary butylenes and isobutylene are polymerized by passage over asolid granular catalyst, comprising phosphoric acid absorbed on clay orother inert material, at 350-500 F. and around 40 atmospheres. Underthese conditions, when the charge stream contains 30% of secondarybutylenes. and 15% of isobutylene, approximately 67% of the olefins aren-ButyZene-isobutylene codimer properties and composition Mean molecularweight 112.2 Specific gravity, 60/60 F 0.735 Refractive index, n 1.4200True boiling range, F 212-240 ASTM distillation, Fz

Initial 210 10% 216 50% 230 90% 231 End 252 Freezing point, F Below -'76Flash point (Tag), "F 32 Color (Saybolt) 30 Olefin content, percent Over99 Total isooctene content, percent eOver 98 Distribution of isooctenes,

percent by weight:

2,2,3-trimethylpentenes 21 2,2,4-trimethylpentenes 102,3,3-trimethylpentenes 11 2,3,4-trimethylpentenes 47 Dimethylhexenes 10By means of our proces we are able to produce sensitive motor fuels. ofhigh performance number from virtually any secondary olefin-tertiaryolefin copolymer containing a substantial proportion of componentsboiling between about 100' and 400 F. at one atmos here, the usualgasoline boiling range. process are copolymers of mixtures containing atleast one olefin from the group comprising propylene, secondarybutylenes, and secondary amylenes, and at least one olefin from thegroup comprising iso'butylene, 2-methyl-l-butene, and Z-methyl-Z-butene.

In carrying out our invention, we selectively carbonylate a secondaryolefin-tertiary olefin oopolymer, such as the n-butylene-isobutylenecodimer described above, by contacting it with a mixture of hydrogen andcarbon monoxide having a molar ratio between about 05:1 and 5:1 at atemperature between about 200 and 500 F., a pressure between about 50and 300 atmospheres, and a liquid space velocity between about 0.05 andper hour, in the presence of a catalyst comprising cobalt and/or iron.We prefer to carry out the. reaction between about 275 and 425 F.,optimally between 375 and 425 at a pressure around 200 atmospheres andwith a mixture of hydrogen and carbon monoxide having a molar ratiobetween about 1:1 and 3:1. Under these conditions, between 10 and 60% ofn-butylene-isobutylene codimer is converted into nonyl aldehydes andalcohols in a reaction time between about 30 and 120 minutes.

Catalysts comprising cobalt and/or iron are suitable for the selectivecarbonylation reaction of our invention. The catalyst may be used in thepure, finely divided form; or it may be supported on powdered orpelleted inert carriers, such as silica, pumice, or kieselguhr; or itmay be added to the feed mixture in the form of metal carbonyls, oroil-soluble salts of organic acids, such as the naphthenates, stearates,laurates,

Especially suited for our benzoates, phthalates, and the like. Variouspromoters, such as thoria, magnesia, and the like, may be combined withthe catalytic material, and various non-carbonyl-forming metals, such assilver, copper, and the like, may be incorporated in the catalyst torepress the formation of iron or cob-alt carbonyls, which tend todissolve in the reaction mixture, and to be carried out of the reactorwith the reaction product. The use of hydrogen in, greater than.equimolar ratio, based on carbon monoxide, is also advantageous inretarding carbonyl formation. Operation at the higher temperatureswithin the preferred range also tends to minimize the loss of catalystfrom the reactor. For example, we have found that a reaction mixture,after reaching" equilibrium wit an edu molar "i ture of hvdroeen andcarbon monoxide at 3,000 lb./in. and 265 F., contains up to about 30pounds of dissolved cobalt per thousand gallons; at F. it contains up toabout 16 pounds per thou and gallons; and at 400 I. it contains lessthan one pound per thousand gallons.

The reaction may be carried out either batchwise or in flow equi ment.In the former case, the catalyst is most conveniently added to thecharging stock in the form of a slurry. In the latter case, the catalystmay satisfactorily be used as a fixed bed; or alternatively it may beadded to the charging stock in the form of the metal carbonyls oroil-soluble organic-acid salts, in which case the fixed bed may be usedor omitted as de ired. Cooling of the reactor may conveniently b":accomplished. by recycling either the liquid pro uct or the gaseouseflluent. The hydrogen-carbon monoxide mixture is preferably supplied tothe flow equipment at a space velocity between about 20 and 1000 volumesof gas, measured at standard temperature and pressure, per volume ofcatalyst zone per hour.

In the carbonylation stage, a portion of the olefinic charging stock isconverted into aldehydes and alcohols. The remainder of the olefiniccharge is resistant to carbonylation; and inay be converted byhydrogenation into a sensiti e gasolinc of high performance number. Suchhydrogenation may be effected in part during the carbonylation reactionif the carbonylation is carried out under severe conditions. Thehydrogenation may then be completed by subjecting the crude product tothe action of hydrogen in the presence of a hydrogenation catalyst suchas nickel, iron, copper, copper chromite, and the like, or mixturesthereof, suitably at temperatures between about 150 and 700 F. and atpre sures above about 50 atmospheres. First, however, it is desirable toremove substantially all carbon monoxide from the carbonylation productby suitable means, such as by purging with hydrogen or an inert gas, orby washing the liquid successively with an acid and with water.

If desired, the non-carbonylated olefing may be hydrogenated selectivelyto paraffins without simultaneous hydrogenation of the aldehydes, in thepresence of nickel, iron, or copper catalysts, or the like, attemperatures between about and F. and at pressures below about 75atmospheres. After the hydrogenation step, the gasoline and by-productfractions may be separated conveniently by conventional means, such asby extraction with a selective solvent, by extractive distillation, byazeotropic distillation, or by fractional distillation.

Alternatively. the aldehydes may be selectively hydrogenated in thepresence of a cobalt catalyst, suitably at a temperature between about350 and 600 F., a pressure between about 500 and 1500 pounds per squareinch, and a liquid space velocity between about 0.2 and 2.0 per hour, asdisclosed in the copending Burney-Cerveny joint application, Serial No.788,347, filed November 29, 1947, now forfeited in favor of acontinuation-in- ,part thereof, Serial No. 223,124, filed April 26,1951; and after separation of the resulting alcohols, suitably bydistillation, the olefins left 'thereby may be converted into a highquality motor fuel by hydrogenation in the presence of a conventionalhydrogenation catalyst, such as nickel. Mild conditions are suitable;for example, temperatures between about '75 and 150 and pressures belowabout 25 atmospheres may be used satisfactorily.

As a further alternative, prior to the hydrogenation step, thecarbonylated and non-carbonylated groups of 'compoundsmay be separatedby suitable means, such as by extraction'with a selective solvent, byextractive distillation, by

azeotropic distillation, or by fractional distillation, after which thenon-carbonylated materials I may be converted into a superior motor fuelby hydrogenation, suitably under the mild conditions defined above.

The attached flow sheet illustrates a continuous process for carryingout our invention. Olefin copolymer, supplied through line I I, isinjected by pump I2 through heat exchanger I3 into reactor I4, which ismaintained at a pressure between about 100 and 300 atmospheres,preferably about 200 atmospheres, and a temperature between about 200and 500 F., preferably between about 375 and 425 F. The rate ofinjection of copolymer is suitably between about 0.2 and 10 volumes perhour per unit volume of reaction zone, and preferably between about 0.5and 1 per hour. The reactor is packed with a suitable catalyst, such asmetallic cobalt supported on an inert siliceous material, arranged insuch manner that efiicient contact is obtained between the liquidhydrocarbon and the reactant gases. Makeup catalyst. suitably metalcarbonyls, such as cobalt or iron carbonyl, or oil-soluble organic-acidsalts, such as iron or cobalt stearates or naphthenates, may be addedthrough line I 5 to the copolymcr stream in line I I, in order tocompensate for any loss of catalyst from the reactor through carbonylformation therein, or through mechanical losses; Alternatively, solidcatalyst may be omitted from the reactor altogether, and the totalcatalyst requirements may be supplied with the charging stock in theform of metal carbonyls (suitably between about 0.1 and 2%-by weight) ormetal salts of organic acids'(suitably between about 0.1 and by weight).The reacted liquid stream and the residual gas stream are withdrawn fromthe base of the reactor to high-pressure separator I 6. 'Here, thestream is divided into liquid-phase and gas-phase streams, which flowseparately through coolers I1 and I8 respectively. The cooled gas streamfrom cooler I1 is expanded through valve I9 into low-pressure separator20, where condensed liquids are removed. The gas stream emerging fromseparator is again divided, part of it flowing through valve 2I tocompressor 22, from which it is recycled to reactor I4, and theremainder being purged through valve 23 as required to prevent thebuild-up of inerts in the gas stream. The liquid from cooler I8 isdivided into two streams. One stream is recycled through valve 24, pump25, and heat exchanger I3 to, reactor I 4 for the purpose of controllingthe temperature therein during the exothermic reaction between thecopolymer stream, hydrogen, and carbon monoxide. The rate of recycle maybe adjusted to maintain the desired temperature, the cooling liquidbeing introduced at the top of the reactor or at such points within itas may be required to control localized heating. The other liquid streamfrom cooler I8 flows through blow-down valve 26 to low-pressureseparator 21, where dissolved gases are flashed 01f into separator 20.

The mixture of hydrogen and carbon monoxide required for reactor I4 issupplied from reformer furnace 28, wherein a hydrocarbon gas, such asnatural gas or a refinery gas, introduced through line 29, is reformedwith steam, introduced through line 30, to'produce hydrogen, carbonmonoxide, and carbon dioxide." Carbon dioxide is optionally introducedthrough line 3I 'into'the feed gas stream to increase the ratio ofcarbon monoxide to 'hydrogen'in the product gas stream. The reformerproduct gases flow through cooler 32 into separator 33, wherewater iswithdrawn, and from the separator into absorber 34, where the carbondioxide is scrubbed out with aqueous monoethanolamine. The resultingcarbon dioxide-monoethanolamine solution passes through line 35, pump36, and heater 3! intothe top of stripper 38, where carbon dioxide isremoved by reboiler 39. The carbon dioxide stream emerges overheadthrough cooler 40 into separator M, from which condensed liquids arerefluxed to the top of stripper 33. The carbon dioxide from separator 4|is withdrawn through line 42, and may be recycled to reformer 28 throughline 3|, if desired, to increase the ratio of carbon monoxide tohydrogen in the reformer product gas. Regenerated monoethanolaminesolution flows from the bottom of stripper 38, and is recirculatedthrough cooler 43, line 44, and pump 45. to the top of absorber 34. Themixture of gases emerging from absorber 34 is in the ratio of about 0.5to 5 volumes of hydrogen per volume of carbon monoxide, and ispreferably in the range of about 1:1 to 3:1. This mixture flows intocompresser 22, by which it is injected into reactor I4, suitably at therate of about 0.5 to 20. volumes, measured at standard temperature andpressure, per volume of reaction zone per hour. The preferred range isfrom about 1.3 to 2 times the space velocity of the liquid feed.

The liquid streams from separators 20 and 2'! are combined in line 45and transferred by pump 4? through line 48 and heat exchanger 49 intohydrogenation reactor 50. This liquid stream comprises a crude mixtureof aldehydes, alcohols, and non-carbonylated olefins, and ordinarilycontains minor proportions of the catalyst from the previous stage,either in the form of the metal carbonyl, oil-soluble metal salts, orsuspended solids. If desired, the liquid stream may be subjected toadditional process steps to remove the catalyst before the liquid isintroduced into reactor 50. The liquid stream may suitably be scrubbedwith a dilute acid, such as sulfuric acid, and then with water; or itmay be treated with hydrogen or other inert gases at elevatedtemperatures, for example, above about F., in order to destroy metalcarbonyls, and the precipitated metal may then be removed by filtrationor centrifugation (apparatus not shown). The bydrogenation reactor 50 ispacked with a suitable hydrogenation catalyst, comprising nickel, iron,copper, or the like, preferably on an inert sup port. The reactionconditions are adjusted according to the type of catalyst used; withfinely divided metallic .nickel catalyst, for example, the preferredpressures are of the order of magnitude of around 60 atmospheres and thetemperatures are between about 150 and 300 F., in order to hydrogenatesubstantially all of the aldehydes to alcohols, and to produce saturatedcompounds from the unreacted olefins,

Hydrogen for reactor 50 is conveniently prepared by reforming ahydrocarbon gas with steam to produce a mixture of hydrogen and carbonmonoxide, then subjecting the mixture to the water-gas shift reaction toconvert the carbon monoxide to carbon dioxide, and finally scrubbing outthe carbon dioxide, leaving a purified hydrogen stream. A hydrocarbongas and steam are introduced through line into reformer 52, where theyare converted by the action of a ceriapromoted nickel catalyst at 1800F. into a mixture of hydrogen, carbon monoxide, carbon dioxide, andunreacted steam. The gases are then introduced through line 53 intoshift converter 54. Therein, the gases are contacted with a suitablecatalyst, such as iron, at a temperature between about 500 and 1000 F.,whereby substantially all of the carbon monoxide is converted intocarbon dioxide. The treated gases emerge through cooler 55 intoseparator 58, from which water is withdrawn, and are then introducedinto the bottom of absorber 51, where the carbon dioxide is scrubbed outwith aqueous monoethanolamine. The carbon dioxide-monoethanol aminesolution emerging from the bottom of absorber 51 flows through line 58,pump 36, and heater 3'! into stripper 38; and regeneratedmonoethanolamine solution is supplied from stripper 38 through cooler43, line 58, and pump 60 to the top of absorber 51.

A purified hydrogen stream emerges overhead from absorber 5'! throughline 6!. If desired, any traces of carbon oxides remaining in thehydrogen may be removed by subjecting it to methanation, underconditions described in the prior art (apparatus not shown). Forexample, the hydrogen may be passed ever a nickel catalyst at atemperature between about 350 and 650 F. The purified hydrogen fiowsinto compressor $2, and after compression is introduced into reactor 50through line 63. The hydrogen passes upward through the downward-flowingliquid stream, the

aldehydes therein being converted thereby into alcohols, and the olefinsbeing converted into the corresponding saturated hydrocarbons. Excessgas is withdrawn at the top of the reactor through cooler 54 andexpanded through valve 55 into low-pressure separator 55, from which thegases are withdrawn and purged in part through line B1 to prevent theaccumulation of inert constituents, and recycled in part if desired,suitably to reformer 52 (lines not shown) From the bottom of reactor 50.liquid is withdrawn through line 68 into cooler 69. The cooled liquidstream is divided, part of it being recycled through valve [0, pump H,line 48, and heat exchanger 00 t. reactor 50 to assist in maintainingthe reaction temperature at the desired level, while the remainder ofthe stream is reduced in pressure to around one atmosphere through valve12 and allowed to flow into low-pressure separator '53, where thedissolved gases are flashed off and vented or recycled as desired.

The liquid streams from separators 66 and 13 are combined in line M andtransferred by pump 15 through heater 16 into fractionating column H atan intermediate point. The hydrocarbon constituents are fractionallydistilled overhead by reboiler l8, and are condensed in cooler 19. Thecondensate flows into reflux drum 80, from which a portion is refluxedthrough valve 8| to the top of the column, and the remainder iswithdrawn through valve 82 as the sensitive, high performance-numbermotor-fuel fraction.

The bottoms stream from column 11, comprising alcohols and otheroxygenated hydrocarbon derivatives, is withdrawn through cooler 83 andsent to storage or further processing. The mixed alcohols and oxygenatedcompounds may be used as such; or they may be subjected to furtherfractionation to isolate substantially pure components; or, if desired,they may be reconverted to olefins by treatment in the vapor phase overalumina at temperatures around 900 F., and the olefins may then berecycled to reactor I4.

t will be noted that reactor I4 is shown with liquid and gas flowingconcurrently downward, whereas in reactor 50 the liquid stream flowsdownward countercurrent to the gas stream. It is intended that either ofthese flow systems may be used in either reactor. Moreover, a thirdmodification, in which the liquid and gas flow upward in parallel, mayalso be used in either reactor.

The following specific examples will more clearly illustrate ourinvention:

EXAMPLE I A supported catalyst containing 8.1% cobalt was prepared bycommingling a solution of cobalt nitrate with 10-20 mesh Filtros (bondedsilica) and evaporating to dryness, then decomposing the nitrate to theoxide by heating, subsequently charging the material into astainlesssteel reactor having a catalyst zone with a lengthto-diameterratio of 26.6, and finally reducing the cobalt oxide with hydrogen at700 F. and atmospheric pressure.

Three series of experiments were then carried out by passingn-butylene-isobutylene codimer and an equimolar mixture of hydrogen andcarbon monoxide concurrently downward through the reactor at an averagepressure around 3,000 pounds per square inch and an average spacevelocity around 0.45 volume of codimer per volume of catalyst zone perhour. The gas mixture was introduced at a space velocity around 200volumes of gas, measured at standard temperature and pressure, pervolume of catalyst zone per hour. After emerging from the reactor, theefiiuent liquid was cooled, flashed to atmospheric pressure, and removedfrom the system.

In each of the experiments, after a quantity of the efiiuent liquid hadbeen accumulated, it was passed again through the reactor one or moretimes under similar conditions, without being subjected to intermediateprocessing steps, in order to determine the effect of longer exposure tothe reaction conditions.

The results of the experiments were as follows:

Experiment N o. 11

Pass No 1 2 3 4 'leznncrature, F 412 405) 405 402 Liqni'l Sr). VBL, hr?i 0. 41 0. 4G 0. .6 (l. M Product composition, vol. per nt:

Hvdr-t on G9. 8 02. l 6 17.2 21. 5 28. 4 4. 8 8. (i ll. 9 1. 3 1.8 3. 90. 49 1.30 l. 71

Experiment No. 12

Pass No 1 2 3 4 Temperature, F.

Liquid sp. vel., hr. 1

Product composition Hydrocarbons Aldehydes Alcohols Experiment No. 13

Pass No 1 2 Temperature, "F Liquid sp. vel., Ina- Product composition,vol. percent:

Hydrocarbons Aldehydes. Alcohols High-boilers Soluble Co in product,lb./l,000 gal g O r-z s i p33 HOD-WED ADD- Performance NumberSensitivity ASTM OFR Motor Research Codimer charging stock 59. 4 91. 231. 8 Recovered olefins 59. 7 91. 81.8 Hydrogenated codimer 81. 4 97. 616. 2 Hydrogenated recovered olefins... 79.1 103. 6 24. 5

Motor fuels of superior performance number and sensitivity were alsoprepared by reacting n-butylene-isobutylene codimer with carbon i fmonoxide and hydrogen 1n various other ways,

as described in the following examples, and subsequently hydrogenatingthe carbonylation-resistant olefins.

EXAMPLE II Inert, 4-8 mesh Filtros was packed in a reactor z one havinga length-to-diameter ratio of 26.6. Two series of experiments were thencarried out by passing n-butylene-isobutylene codimer containing cobaltnaphthenate in solution downward through the reactor concurrently withan equimolar mixture of hydrogen and carbon monoxide at an averagepressure around 2,800 pounds per square inch and an average spacevelocity around 0.4 volume of codimer per volume of Filtros zone perhour. The gas mixture was introduced at a space velocity around 200volumes of gas, measured at standard temperature and pressure, pervolume of Filtros zone per hour. In each experiment, the effluent liquidwas cooled, flashed to atmospheric pressure, and removed from thesystem; and the accumulated efiiuent liquid was passed through thereactor three additional times under the same conditions, withoutintermediate processing steps, and without the introduction ofExperiment N0. 16

Pass No 1 2 3 4 Catalyst concentration, 1b. (Jo/1,000 gaL 4. 4Temperature, F 394 409 402 415 Liquid sp. vel., hrr 0.46 0.37 0.44 0.39-Product composition, vol. percent:

Hydrocarbons 79. 2 68. l 63. 9 58. 3 Aldehydes 18. 5 20. 6 24. 3 24. 5Alcohols 0 5. 7 6. 5 7. 7 High-boilers 0.5 1.8 2. l 3. 9 Soluble Co inproduct, lb./1,000 gal. 1.08 0.41 0.47 0. 47

Experiment No. 18

Pass No 1 2 3 4 Catalyst concentration, lb. Oo/1,000 gal. Temperature, FLiquid space velocity, hrr Product composition, vol. percent:

Hydrocarbons Aldehydes.

High-boilers Soluble Co in product, lb./l,000 ga EXAMPLE III per pass.The results were as follows:

Experiment N0. 25

Pass N0 1 2 3 Catalyst concentration, lb. Co/l,000 gal 1. 6BTemperature, F 326 329 327 Pressure, lb./in. 3, 000 3, 000 3, 000Product compo ition, vol. percent:

Hydrocarbons 65. 4 58. 5 59. 2 Aldehydes. 18.1 21. 3 24.7 Alcohols 0..2. 7 High-boilers 1.6 6 5 2 Experiment No 23 21 24 No. of passes 3 2 3Catalyst concentration, lb. Co/1,000 gal..- 6. 6 5. 8 1.66 Avg.temperature "F 402 330 405 Avg. pressure, lb./1n. 3,000 2, 440 2, 915Final product compositlon, vol. percent:

Hydrocarbons 33. 3 48. 4 64. 0 Aldehydes 21. 9 24. 1 23. 6 Alcohols 29.210. 6 6. 3 High-boilers 10. 3 9. 8 2. 4

The foregoing examples are submitted only as illustrations of convenientand advantageous methods for carrying out the process of our invention,and are not intended to limit the broad applicability thereof in anyway. It is to be distinctly understood that any modifications orequivalents that would ordinarily occur to those skilled in the art areto be considered as lying within the scope of our invention.

In accordance with the foregoing specification, we claim as ourinvention:

We claim:

1. In a process for producing a superior motor fuel from a secondaryolefin-tertiary olefin copolymer, said copolymer containing asubstantial 11 proportion of gasoline-boiling-range components, thesteps which comprise contacting said copolymer with carbon monoxide andhydrogen in the presence of a catalyst containing as the activeconstituent a metal selected from the group consisting of cobalt andiron under conditions of temperature and pressure whereat a portion, butnot all, of said gasoline-boiling-range components are converted intooxygenated derivatives, contacting the resulting reaction product withhydrogen under hydrogenating conditions in the presence of a catalysteffective for the hydrogenation of the unconverted portion of saidcopolymer, whereby the unconverted portion of saidgasoline-boiling-range components are converted into a saturated motorfuel of improved sensitivity and performance number, and separating saidmotor fuel therefrom.

2. The process of claim 1 wherein said copolymer is a copolymer of anolefin mixture comprising a, secondary butylene and isobutylene.

3. The process of claim 1 wherein said copolymer is a copolymer of anolefin mixture comprising propylene and isobutylene.

4. The process of claim 1 wherein said copolymer is a copolymer of anolefin mixture comprising a secondary butylene and a tertiary amylene.

5. The process of claim 1 wherein said copolymer is contacted withcarbon monoxide and hydrogen in the presence of metallic cobalt.

6. In a process for producing a superior motor fuel from a secondaryolefin-tertiary olefin copolymer, said copolymer containing asubstantial proportion of gasoline-boiling-range components, the stepswhich comprise contacting said copolymer with carbon monoxide andhydrogen in the presence of a catalyst containing cobalt as the activeconstituent under conditions of temperature and pressure whereat aportion, but not all, of said gasoline-boiling-range components areconverted into oxygenated derivatives, separating the unconvertedportion of said gasoline-boilingrange components from the resultingreaction product, and contacting said unconverted portion with hydrogenunder hydrogenating conditions in the presence of a catalyst effectivefor the hydrogenation thereof, whereby said portion is converted into asaturated motor fuel of improved sensitivity and performance number.

7. In a process for producing a superior motor fuel from agasoline-boiling-range copolymer of an olefin mixture, said olefinmixture consisting predominantly of a secondary olefin and a tertiaryolefin, the steps which comprise contacting said copolymer with carbonmonoxide and hydrogen having a ratio between about 0.5 and 5 moles ofhydrogen per mole of carbon monoxide in the presence of a cobaltcatalyst at a temperature between about 200 and 500 F. and a pressureabove about 50 atmospheres, whereby a portion, but not all, of saidcopolymer is converted into oxygenated derivatives, separating theunconverted portion of said copolymer from the result- 12 ing reactionproduct, and contacting said unconverted portion of said copolymer withhydrogen under hydrogenating conditions in the presence of a catalysteffective for the hydrogenation thereof, whereby said portion of saidcopolymer is converted into a saturated motor fuel of improvedsensitivity and performance number.

8. In a process for producing a superior motor fuel from agasoline-boiling-range copolymer of an olefin mixture, said olefinmixture consisting predominantly of a secondary olefin and a tertiaryolefin, the steps which comprise contacting said copolymer with carbonmonoxide and hydrogen having a ratio between about 0.5 and 5 moles ofhydrogen per mole of carbon monoxide in the presence of a cobaltcatalyst at a temperature between about 200 and 500 F. and a pressureabove about 50 atmospheres, whereby a portion, but not all, of saidcopolymer is converted into oxygenated derivatives; contacting theresulting reaction product with hydrogen at a temperature between aboutand 700 F. and a pressure above about 50 atmospheres in the presence ofa catalyst selected from the group consisting of nickel, iron, copper,and copper chromite, and separating a saturated motor fuel of improvedsensitivity and performance number therefrom by distillation.

9. A process for producing a superior motor fuel from an-butylene-isobutylene codimer which comprises contacting said codimerwith an approximately equimolar mixture of carbon monoxide and hydrogenin the presence of a cobalt catalyst at a temperature between about 275and 425 F. and a pressure between about 50 and 300 atmospheres;contacting the resulting product with hydrogen in the presence of-anickel hydrogenation catalyst at a temperature between about 150 and 700F. and a pressure above about 50 atmospheres; and subsequentlyfractionally distilling the reaction product and separating therefrom asensitive motor fuel of improved performance number.

DONALD E. BURNEY. BERNARD H. SHOEMAKER.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,138,881 Pyzel Dec. 6, 19382,147,268 Pyzel Feb. 14, 1939 2,327,066 Roelen Aug. 17, 1943 2,403,524Hagemann July 9, 1946 2,418,899 Pevere et a1 Apr. 15, 1947 2,437,600Gresham et al Mar. 9, 1948 FOREIGN PATENTS Number Country Date 873,891France Mar. 16, 1942

1. IN A PROCESS FOR PRODUCING A SUPERIOR MOTOR FUEL FROM A SECONDARYOLEFIN-TERTIARY OLEFIN COPOLYMER, SAID COPOLYMER CONTAINING ASUBSTANTIAL PROPORTION OF GASOLINE-BOILING-RANGE COMPONENTS, THE STEPSWHICH COMPRISE CONTACTING SAID COPOLYMER WITH CARBON MONOXIDE ANDHYDROGEN IN THE PRESENCE OF A CATALYST CONTAINING AS THE ACTIVECONSTITUENT A METAL SELECTED FROM THE GROUP CONSISTING OF COBALT ANDIRON UNDER CONDITIONS OF TEMPERATURE AND PRESSURE WHEREAT A PORTION, BUTNOT ALL, OF SAID GASOLINE-BOILING-RANGE COMPONENTS ARE CONVERTED INTOOXYGENATED DERIVATIVES, CONTACTING THE RESULTING REACTION PRODUCT WITHHYDROGEN UNDER HYDROGENATING CONDITIONS IN THE PRESENCE OF A CATALYSTEFFECTIVE FOR THE HYDROGENATION OF THE UNCONVERTED PORTION OF SAIDCOPOLYMER, WHEREBY THE UNCOVERTED PORTION OF SAID GASOLINE-BOILING-RANGECOMPONENTS ARE CONVERTED INTO A SATURATED MOTOR FUEL OF IMPROVEDSENSITIVITY AND PERFORMANCE NUMBER, AND SEPARATING SAID MOTOR FUELTHEREFROM.